CH258174A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents
Process for the preparation of a new oxyhydrophenanthrene derivative.Info
- Publication number
- CH258174A CH258174A CH258174DA CH258174A CH 258174 A CH258174 A CH 258174A CH 258174D A CH258174D A CH 258174DA CH 258174 A CH258174 A CH 258174A
- Authority
- CH
- Switzerland
- Prior art keywords
- ethyl
- methoxy
- propyl
- carboxylic acid
- phenanthrene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- -1 1-ethyl-2-n-propyl Chemical group 0.000 claims description 3
- PDGGPUNHFUDIHX-UHFFFAOYSA-N CCCC(CC1)(C(CC)C(C=CC2=C3)=C1C2=CC=C3OC)C(O)=O Chemical compound CCCC(CC1)(C(CC)C(C=CC2=C3)=C1C2=CC=C3OC)C(O)=O PDGGPUNHFUDIHX-UHFFFAOYSA-N 0.000 claims description 3
- 206010067572 Oestrogenic effect Diseases 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001076 estrogenic effect Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 230000001225 therapeutic effect Effects 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QUNNGNJYPJAUGU-UHFFFAOYSA-N CCCC(CC1)(C(CC)C(C=CC2=C3)=C1C2=CC=C3OC)C(OC)=O Chemical compound CCCC(CC1)(C(CC)C(C=CC2=C3)=C1C2=CC=C3OC)C(OC)=O QUNNGNJYPJAUGU-UHFFFAOYSA-N 0.000 description 1
- 241001101998 Galium Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/30—Unsaturated compounds
- C07C62/34—Unsaturated compounds containing ether groups, groups, groups, or groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines neuen Oxyhydrophenanthren-Derivates. Es wurde gefunden, dass man zu einem neuen Oxyhydrophenanthren-Derivat gelan gen kann, wenn man ein 1-Äthyl-2-n-propyl-7- me@thoxy-1,2,3,4-tetrahydro-phenanthren, das in 2-Stellung einen durch Hydrolyse in die, freie Ca.rboxyl,grupp e überführbaren Substi- tuenten, z.
B. eine veresterte Carboxylgruppe, enthält, zwecks Bildung einer freien Carb- oxylgruppe mit hydnolysierenden Mitteln be handelt.
Das noch nicht bekannte Endprodukt des Verfahrens, die 1-Äthyl-2-n-propyl-7-meth oxy-1,2,3,4-tetrahydro-phenanthren-2-carbon- säure vom F. 206-207 , zeigt sowohl bei par- enteraler als auch bei oraler Applikation eine ausserordentlich hohe oestrogene Wirkung. Es soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung thera peutisch verwendbarer Verbindungen dienen.
Für die Überführung des. Substituenten in 2-Stellung in die freie Carboxylgruppe verwendet man beispielsweise anorganische Basen, wie Alkali- oder Erdalkalihydroxyde.
Die Ausgangsstoffe werden z. B. erhalten aus 1-Keto-2-n-p@ropyl-7-methoxy-1,2,3,4- tetrahydro-phenanthrenen, die in 2-Stellung einen durch Hydrolyse in -die freie Carboxyl- gruppe überführbaren Substituenten auf weisen, durch Grignandierung mit einem Äthylmagnesiumh,alogenid, Wasserabspaltung aus dem so erhaltenen 1-Äthyl-l-ogy-2-n- propyl- 7-methoxy,-1,2,3,
4-tetrahydro-phen- a nthren-Derivat und anschliessende Hydrie rung der gebildeten Doppelbindung. <I>Beispiel:
</I> 3,3 Gewichtsteile 1-Äthyl-2-n-propyl-7- methoxy -1,2,3,4- tetrahydro- phenanthren - 2- carbonsäuremethylester vom F. 111-112 und der Formel
EMI0001.0059
w erden in einer Mischung von 16,5 Gewichts teilen Kaliumhydroxyd, 5 Volumteilen Wasser und 10 Volumteilen Alkohol auf 160 erhitzt. Nach dem Verdampfendes.
Alkohols kri3talli- siert noch in der Wärme das galiumsalz der Carbonsäure aus. Dieses nimmt man in 100 Volumteilen Wasser) auf, worauf sich nach kurzer Zeit das schwer lösliche Kaliumsalz ausscheidet.
Durch Zersetzen. mit verdünnter Salzsäure wird daraus die oesitrogen wirksame 1-Äthyl - 2 -,n-p@nopy1'-7-methoxy-1,2,3,4-t-etra- hydro@phenanthren-2-carbonsäure der Formel
EMI0001.0082
erhalten, die nach Umlösen aus Methanol bei 206-207 schmilzt.
Den Ausgangsstoff erhält man z. B. wie folgt: 6,5 Gewichtsteile 1-Keto-2-n-propyl-7- methoxy, -1,2,3,4 - tetrahytdro - phenanthren - 2- car#bonsäuremethyl@ester lässt man mit einer Grignard-Lösung, hergestellt aus 0,6 Ge- wicUtsteil Magnesium und 2 Volumteilen Äthylbromid, reagieren,
kocht 8 Gewichts teile des so gewonnenen 1-Äthyl-l-pxy-2-n- propyl -1,2,3,4 - tetrahydro - phenanthren - 2- carbonsä:uremethylestera vom F. 127-128 zwecks Wa."sserabspaltung in einer Lösung von 0,3 Gewichtsteil Jod in 40 Volumteilen Chloroform und hydriert 1 Gewichtsteil:
der Äthyliden-Verbindung in 30 Volumteilen Alkohol in Gegenwart von 0,1 Gewichtsteil eines Plahnkatalysatoru zum 1-Äthyl-2-n- propyl - 7 -methoxy -1,2.,3,4 - tetrahydro-phen- anthren-2-caTbonsäuremethylester vom F. 111 bis 112 .
Process for the preparation of a new oxyhydrophenanthrene derivative. It has been found that a new oxyhydrophenanthrene derivative can be obtained if a 1-ethyl-2-n-propyl-7-methoxy-1,2,3,4-tetrahydrophenanthrene, which is shown in FIG -Position a by hydrolysis in the, free Ca.rboxyl, group e convertible substituents, z.
B. an esterified carboxyl group contains, in order to form a free carboxyl group with hydrolyzing agents.
The as yet unknown end product of the process, the 1-ethyl-2-n-propyl-7-methoxy-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid of F. 206-207, shows both an extraordinarily high estrogenic effect with parenteral and also with oral administration. It should find therapeutic use or serve as an intermediate for the preparation of therapeutically useful compounds.
For example, inorganic bases, such as alkali or alkaline earth metal hydroxides, are used to convert the substituent in the 2-position into the free carboxyl group.
The starting materials are z. B. obtained from 1-keto-2-np @ ropyl-7-methoxy-1,2,3,4-tetrahydro-phenanthrenes, which in the 2-position have a substituent which can be converted into the free carboxyl group by hydrolysis, by Grignanding with an ethylmagnesiumh, alogenid, elimination of water from the 1-ethyl-l-ogy-2-n-propyl-7-methoxy, -1,2,3,
4-tetrahydro-phen-anthene derivative and subsequent hydrogenation of the double bond formed. <I> example:
3.3 parts by weight of 1-ethyl-2-n-propyl-7-methoxy -1,2,3,4-tetrahydro- phenanthrene-2-carboxylic acid methyl ester of F. 111-112 and the formula
EMI0001.0059
w are heated to 160 in a mixture of 16.5 parts by weight of potassium hydroxide, 5 parts by volume of water and 10 parts by volume of alcohol. After the evaporation.
Alcohol crystallizes out the galium salt of the carboxylic acid even when it is warm. This is taken up in 100 parts by volume of water, whereupon the poorly soluble potassium salt separates out after a short time.
By decomposing. with dilute hydrochloric acid, it becomes the oesitrogenically active 1-ethyl-2 -, n-p @ nopy1'-7-methoxy-1,2,3,4-t-etra-hydro @ phenanthrene-2-carboxylic acid of the formula
EMI0001.0082
obtained which melts at 206-207 after redissolving from methanol.
The starting material is obtained z. B. as follows: 6.5 parts by weight of 1-keto-2-n-propyl-7-methoxy, -1,2,3,4-tetrahytdro-phenanthrene-2-carboxylic acid methyl ester is left with a Grignard solution , made from 0.6 part by weight of magnesium and 2 parts by volume of ethyl bromide, react,
boils 8 parts by weight of the 1-ethyl-1-pxy-2-n-propyl -1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid obtained in this way: uremethylestera of F. 127-128 for the purpose of splitting off water in a solution of 0.3 part by weight of iodine in 40 parts by volume of chloroform and hydrogenated 1 part by weight:
the ethylidene compound in 30 parts by volume of alcohol in the presence of 0.1 part by weight of a Plahnkatalysatoru to 1-ethyl-2-n-propyl-7-methoxy-1,2, 3,4-tetrahydro-phen-anthrene-2-carboxylate from F. 111 to 112.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH258174T | 1944-01-10 | ||
| CH250372T | 1944-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH258174A true CH258174A (en) | 1948-11-15 |
Family
ID=25729430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH258174D CH258174A (en) | 1944-01-10 | 1944-01-10 | Process for the preparation of a new oxyhydrophenanthrene derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH258174A (en) |
-
1944
- 1944-01-10 CH CH258174D patent/CH258174A/en unknown
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